CN104059638B - Metal nano particle-doped alkaline earth strontium thiogallate luminescent material and preparation method - Google Patents
Metal nano particle-doped alkaline earth strontium thiogallate luminescent material and preparation method Download PDFInfo
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Abstract
The invention belongs to field of light emitting materials, it discloses a kind of metal nano particle-doped alkaline earth strontium thiogallate luminescent material and preparation method thereof; The chemical general formula of this luminescent material is M
1-xga
2s
4: Ce
x 3+m '
y, wherein, M
1-xga
2s
4: Ce
x 3+for shell, M ' is kernel, represents coated, and M is at least one in Ca, Sr, Ba, and M ' is at least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, and the span of x is 0 & lt; X≤0.2, y is M ' and M
1-xga
2s
4: Ce
x 3+mole ratio, the span of y is 0 < y≤1 × 10
-2.In metal nano particle-doped alkaline earth strontium thiogallate luminescent material of the present invention, introduce M ' metallics, the luminous efficiency of alkaline earth strontium thiogallate luminescent material under same shooting conditions is greatly improved, and radiative wavelength does not change, purity of color and the brightness of launching bright dipping after being stimulated are all higher, can be applied to feds.
Description
Technical field
The present invention relates to field of light emitting materials, particularly relate to a kind of metal nano particle-doped alkaline earth strontium thiogallate luminescent material and preparation method.
Background technology
Field Emission Display (FED) is the flat-panel monitor that a kind of new development is got up, its principle of work and traditional cathode tube similar, be imaging by the fluorescent material on beam bombardment display screen.Compared with other flat-panel monitor (FPD), FED all has potential advantage in brightness, visual angle, time of response, operating temperature range, energy consumption etc.Prepare the preparation that one of key factor of premium properties FED is fluorescent material.The SrGa of Eu doping
2s
4be a kind of tri compound sulfide, compared with oxide compound, better electron acceleration can be provided under the electric field; And relative to some binary sulfides (as SrS, CaS), stable many, but be the focus studied to the raising of its luminous efficiency always.
Summary of the invention
Problem to be solved by this invention is to provide the metal nano particle-doped alkaline earth strontium thiogallate luminescent material that a kind of luminous efficiency is higher, can be used for Flied emission.
Technical scheme of the present invention is as follows:
A metal nano particle-doped alkaline earth strontium thiogallate luminescent material, its chemical general formula is M
1-xga
2s
4: Ce
x 3+m '
y, wherein, M
1-xga
2s
4: Ce
x 3+for shell, M ' is kernel, represents coated, and M is at least one in Ca, Sr, Ba alkaline earth element, and M ', for metal nano particle-doped, is selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, and x is Ce
3+the mole number of ionic replacement M atom, the span of x is 0<x≤0.2, and y is M ' and M
1-xga
2s
4: Ce
x 3+mole ratio, the span of y is 0 < y≤1 × 10
-2; M
1-xga
2s
4: Ce
x 3+for luminescent material, colon ": " is expressed as the doping of Ce.
Described metal nano particle-doped alkaline earth strontium thiogallate luminescent material, preferably, the span of x is 0.001≤x≤0.1, and the span of y is 1 × 10
-5≤ y≤5 × 10
-3.
The invention still further relates to a kind of preparation method of metal nano particle-doped alkaline earth strontium thiogallate luminescent material, comprise the steps:
Will containing after the salts solution of M ', auxiliary agent and reductive agent hybrid reaction, obtained M ' nanometer particle colloid solution;
Described M ' nanometer particle colloid solution is added in the ethanol solution of sucrose or glucose, obtain mixing solutions, and the described mixing solutions confined reaction at 120 ~ 200 DEG C that will obtain, the obtained solution containing CM ', containing the solution of CM ' described in centrifugation, the solid phase obtained is washed, obtains CM ' carbon ball template after drying; Wherein, the mol ratio of expression C coated M ', M ' nanoparticle and CM ' carbon ball template is 1 × 10
-6: 1 ~ 0.4:1, C represent carbon;
According to M
1-xga
2s
4: Ce
x 3+m '
yin each element chemistry metering ratio, measure M, the aqueous ethanolic solution of Ga and Ce salt, and then add described CM ' carbon ball template, stir, then oxalic acid precipitation agent is slowly added, obtain mixing solutions, then regulate the pH value of mixing solutions to be 10 ~ 12, after continuing stirring reaction 2 ~ 8h, filtration, washing, dry sediment, obtain M
1-xga
2(C
2o
4)
4: Ce
x 3+cM ' presoma; Wherein, M
1-xga
2(C
2o
4)
4: Ce
x 3+in CM ', M
1-xga
2(C
2o
4)
4: Ce
x 3+represent shell, C represents center, represents coated, and M ' is kernel; CM ' carbon ball template and M
1-xga
2s
4: Ce
x 3+mol ratio be 0.025:1 ~ 10:1;
Grind described precursor powder even, under being placed in process furnace air atmosphere, in 500 ~ 800 DEG C of pre-burnings 1 ~ 12 hour, carbon is converted into CO
2removing, is cooled to room temperature, then it is even to grind pre-sintered sample, grinding powder is placed in process furnace again, and passes into rare gas element in process furnace, makes to be inert atmosphere in process furnace; Then H is passed into
2s, at 800 ~ 1200 DEG C of calcining 2-10h, is cooled to 500 DEG C of stoppings to pass into H
2s, changes into and passes into rare gas element, under being cooled to normal temperature, stops passing into rare gas element, takes out sample, and evenly, obtain metal nano particle-doped alkaline earth strontium thiogallate luminescent material, the chemical general formula of this luminescent material is M in grinding
1-xga
2s
4: Ce
x 3+m '
y;
In above-mentioned steps, M
1-xga
2s
4: Ce
x 3+for shell, M ' is kernel, represents coated, and M is at least one in Ca, Sr, Ba alkaline earth element, and M ', for metal nano particle-doped, is selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, and x is Ce
3+the mole number of ionic replacement M atom, the span of x is 0<x≤0.2, and y is M ' and M
1-xga
2s
4: Ce
x 3+mole ratio, the span of y is 0 < y≤1 × 10
-2.
The preparation method of described metal nano particle-doped alkaline earth strontium thiogallate luminescent material, preferably, described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride, and the mol ratio of described reductive agent and M ' is 0.5:1 ~ 10:1; In actual use, reductive agent needs to be configured to the aqueous solution, and its concentration is 1 × 10
-4mol/L ~ 1mol/L; Auxiliary agent is at least one in polyvinyl pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate or sodium laurylsulfonate, and the content of addition in the M ' nanometer particle colloid finally obtained of auxiliary agent is 1 × 10
-4g/mL ~ 5 × 10
-2g/mL.
The preparation method of described metal nano particle-doped alkaline earth strontium thiogallate luminescent material, preferably, the time of the salts solution of M, auxiliary agent and reductive agent hybrid reaction is 10 ~ 45min.
The preparation method of described metal nano particle-doped alkaline earth strontium thiogallate luminescent material, preferably, the confined reaction of sucrose or glucose and M ' nanometer particle colloid carries out being with in teflon-lined reactor.
The preparation method of described metal nano particle-doped alkaline earth strontium thiogallate luminescent material, preferably, preferably, the washing process containing the solid phase obtained during the solution of CM ' described in centrifugation: use deionized water successively and repetitive scrubbing is repeatedly successively.
The preparation method of described metal nano particle-doped alkaline earth strontium thiogallate luminescent material, wherein, M, Ga and Ce salt be each self-corresponding nitrate or acetate.
M, Ga and Ce salt aqueous ethanolic solution separately adopts following methods to obtain:
Respectively with the oxide compound of M, Ga and Ce and carbonate for raw material, be dissolved in nitric acid, then to add volume ratio be in the second alcohol and water of 3 ~ 8:1, the aqueous ethanolic solution of the M obtained respectively, Ga and Ce salt; Or respectively with the acetate of M, Ga and Ce, nitrate for raw material, being dissolved in volume ratio is in the second alcohol and water of 3 ~ 8:1, the aqueous ethanolic solution of the M obtained respectively, Ga and Ce salt.
The preparation method of described metal nano particle-doped alkaline earth strontium thiogallate luminescent material, preferably, the mole dosage of described oxalic acid precipitation agent is for getting M with guarantee, Ga and Ce ion precipitates and excessive 25% completely, and its effect is: when reacting according to chemical equation, can ensure M, the precipitation of Ga and Ce ion is complete, excessive effect all precipitates completely in order to ensure all metal ions exactly, and unreacted oxalic acid is solution, can wash away when filtering.
The preparation method of described metal nano particle-doped alkaline earth strontium thiogallate luminescent material, preferably, is adjusted to 10 ~ 12 and adopts ammoniacal liquor to regulate by the pH value of mixing solutions.
The preparation method of described metal nano particle-doped alkaline earth strontium thiogallate luminescent material, preferably, in precursor power, vacuum-drying 2 ~ 10h at described sedimentary drying is 60 ~ 100 DEG C.
The preparation method of described metal nano particle-doped alkaline earth strontium thiogallate luminescent material, preferably, the process furnace in precursor powder preparation process is high temperature box furnace or retort furnace.
The preparation method of described metal nano particle-doped alkaline earth strontium thiogallate luminescent material, preferably, the pre-burning of precursor powder and H
2in S calcination process, rare gas element is argon gas, helium etc., preferred argon gas.
The preparation method of described metal nano particle-doped alkaline earth strontium thiogallate luminescent material, preferably, the span of x is 0.001≤x≤0.1, and the span of y is 1 × 10
-5≤ y≤5 × 10
-3.
The preparation method of metal nano particle-doped alkaline earth strontium thiogallate luminescent material provided by the invention, adopt hydrothermal method to prepare the carbon bead of clad metal nano particle, and then be that template adopts oxalate precipitation method to prepare M with the carbon bead being coated with M ' metal nanoparticle
1-xga
2(C
2o
4)
4: Ce
x 3+cM ' precursor powder, and then calcine, in calcination process, carbon will be converted into CO
2effusion, forms hollow structure, then passes into H
2s gas is calcined, and finally obtains hollow structure, metal nano particle-doped M
1-xga
2s
4: Ce
x 3+m '
yluminescent material.
In above-mentioned metal nano particle-doped alkaline earth strontium thiogallate luminescent material, owing to introducing M ' metal nanoparticle, make alkaline earth strontium thiogallate MGa
2s
4: Ce
3+the luminous efficiency of luminescent material under same shooting conditions is greatly improved, and radiative wavelength does not change, and purity of color and the brightness of launching bright dipping after being stimulated are all higher, can be applied in feds.
The preparation method of metal nano particle-doped alkaline earth strontium thiogallate luminescent material of the present invention, processing step is few, relatively simply; Processing condition are not harsh, easily reach, and cost is low; Do not introduce other impurity, the luminescent material quality obtained is high, can be widely used in the preparation of luminescent material.
Accompanying drawing explanation
Fig. 1 is the luminescent spectrum comparison diagram under the obtained luminescent material of the embodiment of the present invention 4 and the cathode-ray exciting of comparative example luminescent material under acceleration voltage is 1.5KV; Wherein, curve 1 is the Sr being mixed with metal nanoparticle Ag prepared by the present embodiment 4
0.96ga
2s
4: Ce
0.04 3+ag
2.5 × 10the luminescent spectrum of-4 luminescent materials, curve 2 is Sr that comparative example is not mixed with metal nanoparticle Ag
0.96ga
2s
4: Ce
0.04 3+the luminescent spectrum of luminescent material.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1:Ca
0.9ga
2s
4: Ce
0.1 3+cu
1 × 10-4
The preparation of Cu nano particle colloidal sol: take 1.6mg cupric nitrate and be dissolved in the ethanol of 16mL, after dissolving completely, stirs and adds 2mgPVP, then slow instillation 0.4mg sodium borohydride molten obtain in 10mL ethanol 1 × 10
-3the sodium borohydride alcoholic solution 4mL of mol/L, continues stirring reaction 10min, obtains 20mL4 × 10
-4the Cu nanometer particle colloid of mol/L.
The preparation of CCu: take the alcoholic solution that 0.1426g sucrose dissolved prepares sucrose in the dehydrated alcohol of 39.5mL, above-mentioned for 0.5mL colloidal sol is added in the alcoholic solution of sucrose, obtain mixing solutions, mixing solutions being proceeded to 50mL is with in teflon-lined reactor again, add a cover after screwing, in 200 DEG C of reaction 5h, prepare the solution containing CCu, this solution of centrifugation obtains solid formation, 2 times are washed respectively with deionized water and dehydrated alcohol, and solid formation is dry at 75 DEG C, namely CCu carbon ball template is obtained, now the mol ratio of metal nanoparticle Cu and C is 4 × 10
-5: 1.
Take 5.6080gCaO and be dissolved in the Ca (NO that nitric acid obtains 100mL1mol/L
3)
3solution; Take 9.3720gGa
2o
3be dissolved in the Ga (NO that nitric acid obtains 100mL1mol/L
3)
3solution; Take 1.7212gCeO
2be dissolved in the Ce (NO that nitric acid obtains 100mL0.1mol/L
3)
3solution.According to Ca
0.9ga
2s
4: Ce
0.1 3+cu
1 × 10the stoichiometric ratio of-4 pipettes 3.6mL1mol/LCa (NO
3)
2, 8mL1mol/LGa (NO
3)
3and 4mL0.1mol/LCe (NO
3)
3solution, is placed in 100mL beaker and forms nitric acid mixed solution, then takes CCu carbon ball template 120mg and adds in mixed solution, stir.Under magnetic stirring, above-mentioned mixed solution is added drop-wise in 20mL precipitation agent oxalic acid solution (1mol/L), then regulates pH to be 10 by ammoniacal liquor, after reaction 4h, through filtering, deionized water and washing with alcohol, obtain white mass, i.e. Ca after 100 DEG C of vacuum-drying 2h
0.9ga
2(C
2o
4)
4: Ce
0.1 3+cPd
1 × 10-
5precursor powder;
Ground by presoma, be put in atmosphere in 800 DEG C of pre-burning 1h in retort furnace, then in agate mortar, grinding evenly, is placed in corundum crucible, puts into stove, and first logical argon gas 15min, catches up with most air, then pass into H
2s, at 1300 DEG C of calcining 1h, is cooled to 500 DEG C to stop H
2s changes argon gas, stops argon gas under normal temperature, takes out grinding and evenly namely obtains Ca
0.9ga
2s
4: Ce
0.1 3+cu
1 × 10-4 luminescent materials.
Embodiment 2:Sr
0.8ga
2s
4: Ce
0.2 3+au
1 × 10-2
The preparation of Au nano particle colloidal sol: take 41.2mg hydrochloro-auric acid (AuCl
3hCl4H
2o) be dissolved in the deionized water of 10mL; After hydrochloro-auric acid dissolves completely, take 14mg Trisodium Citrate and 6mg cetyl trimethylammonium bromide, and be dissolved in aqueous solution of chloraurate under the environment of magnetic agitation; Take 3.8mg sodium borohydride and 17.6mg xitix is dissolved in 10mL deionized water respectively, obtaining 10mL concentration is 1 × 10
-2the sodium borohydride aqueous solution of mol/L and 10mL concentration are 1 × 10
-2the aqueous ascorbic acid of mol/L; Under the environment of magnetic agitation, first in aqueous solution of chloraurate, add 5mL sodium borohydride aqueous solution, after stirring reaction 5min, in aqueous solution of chloraurate, add 5mL1 × 10 again
-2the aqueous ascorbic acid of mol/L, continue reaction 30min afterwards, obtaining 20mLAu content is 5 × 10
-3the Au nano particle colloidal sol of mol/L.
The preparation of CAu: take the alcoholic solution that 0.0057g sucrose dissolved prepares sucrose in the dehydrated alcohol of 24mL, above-mentioned for 16mL colloidal sol is added in the alcoholic solution of sucrose, obtain mixing solutions, mixing solutions being proceeded to 50mL is with in teflon-lined reactor, add a cover after screwing, in 160 DEG C of reaction 20h, prepare the solution containing CAu, this solution of centrifugation obtains solid formation, 3 times are washed respectively with deionized water and dehydrated alcohol, and dry at 80 DEG C, namely obtain CAu carbon ball template, now the mol ratio of metal nanoparticle Au and C is 0.4:1.
According to Sr
0.8ga
2s
4: Ce
0.2 3+au
1 × 10the stoichiometric ratio of-2 pipettes 6.4mL0.5mol/LSr (CH
3cOO)
2solution, 16mL0.5mol/LGa (CH
3cOO)
3solution and 1.6mL0.5mol/LCe (CH
3cOO)
3solution, is placed in 100mL beaker and forms mixed solution, then takes CAu carbon ball template 1.2mg and adds in mixed solution, stir.Under magnetic stirring, above-mentioned mixed solution is added drop-wise in 25mL precipitation agent oxalic acid solution (0.8mol/L), then regulates pH to be 12 by ammoniacal liquor, after reaction 2h, through filtering, deionized water and washing with alcohol, obtain white mass, i.e. Sr after 60 DEG C of vacuum-drying 8h
0.8ga
2(C
2o
4)
4: Ce
0.2 3+cAu
1 × 10-2 precursor powders;
Ground by presoma, be put in atmosphere in 700 DEG C of pre-burnings 6 hours in retort furnace, then in agate mortar, grinding evenly, is placed in corundum crucible, puts into stove, and first logical argon gas 15min, catches up with most air, then pass into H
2s, at 800 DEG C of calcining 8h, is cooled to 500 DEG C to stop H
2s changes argon gas, stops argon gas under normal temperature, takes out grinding and evenly namely obtains Sr
0.8ga
2s
4: Ce
0.2 3+au
1 × 10-2 luminescent materials.
Embodiment 3:Ba
0.999ga
2s
4: Ce
0.001 3+pd
1 × 10-5
The preparation of Pd nano particle colloidal sol: take 0.22mg Palladous chloride (PdCl
22H
2o) be dissolved in the deionized water of 10mL; After Palladous chloride dissolves completely, take 11.0mg Trisodium Citrate and 4.0mg sodium lauryl sulphate, and be dissolved in palladium chloride aqueous solution under the environment of magnetic agitation; Take 0.38mg sodium borohydride molten in 100mL deionized water, obtaining concentration is 1 × 10
-4the sodium borohydride reduction liquid of mol/L; Under the environment of magnetic agitation, in palladium chloride aqueous solution, add 10mL1 × 10 fast
-4sodium borohydride aqueous solution, afterwards continue reaction 20min, obtaining 20mLPd content is 5 × 10
-5the Pd nano particle colloidal sol of mol/L.
The preparation of CPd: take 6.005g glucose and be dissolved in the alcoholic solution obtaining glucose in the dehydrated alcohol of 36mL, above-mentioned for 4mL colloidal sol is added in the alcoholic solution of glucose, obtain mixing solutions, mixing solutions being proceeded to 50mL is with in teflon-lined reactor, add a cover after screwing, in 120 DEG C of reaction 36h, prepare the solution containing CPd, this solution of centrifugation obtains solid formation, 2 times are washed respectively with deionized water and dehydrated alcohol, and dry at 60 DEG C, namely obtain CPd carbon ball template, now the mol ratio of metal nanoparticle Pd and C is 1 × 10
-6: 1.
According to Ba
0.999ga
2s
4: Ce
0.001 3+pd
1 × 10the stoichiometric ratio of-5 pipettes 19.98mL0.2mol/LBa (NO
3)
2solution, 4mL2mol/LGa (NO
3)
3solution and 0.8mL0.005mol/LCe (NO
3)
3solution, is placed in 100mL beaker and forms nitric acid mixed solution, then takes CPdv480mg and adds in mixed solution, stir.Under magnetic stirring, above-mentioned mixed solution is added drop-wise in 40mL precipitation agent oxalic acid solution (0.5mol/L), then regulates pH to be 11 by ammoniacal liquor, after reaction 3h, through filtering, deionized water and washing with alcohol, obtain white mass, i.e. Ba after 70 DEG C of vacuum-drying 6h
0.999ga
2(C
2o
4)
4: Ce
0.001 3+cPd
1 × 10-5 precursor powders;
Precursor powder to be put in retort furnace in atmosphere in 500 DEG C of pre-burnings 12 hours, carbon will be converted into CO
2removing, in agate mortar, grinding evenly, is placed in corundum crucible, puts into stove, and first logical argon gas 15min, catches up with most air, then pass into H
2s, at 1200 DEG C of calcining 5h, is cooled to 500 DEG C to stop H
2s changes argon gas, stops argon gas under normal temperature, takes out grinding and evenly namely obtains Ba
0.999ga
2s
4: Ce
0.001 3+pd
1 × 10-5 luminescent materials.
Embodiment 4:Sr
0.96ga
2s
4: Ce
0.04 3+ag
2.5 × 10-4:
The preparation of Ag nano particle colloidal sol: take 3.4mg Silver Nitrate (AgNO
3) be dissolved in the deionized water of 18.4mL; After Silver Nitrate dissolves completely, take 42mg Trisodium Citrate and be dissolved in silver nitrate aqueous solution under the environment of magnetic agitation; Take 5.7mg sodium borohydride molten in 10mL deionized water, obtaining 10mL concentration is 1.5 × 10
-2the sodium borohydride aqueous solution of mol/L; Under the environment of magnetic agitation, disposablely in silver nitrate aqueous solution add 1.6mL1.5 × 10
-2the sodium borohydride aqueous solution of mol/L, continue reaction 10min afterwards, obtaining 20mLAg content is 1 × 10
-3the Ag nano particle colloidal sol of mol/L.
The preparation of CAg: take 3.003g glucose and be dissolved in the alcoholic solution preparing glucose in the dehydrated alcohol of 35mL, above-mentioned for 5mL colloidal sol is added in the alcoholic solution of glucose, obtain mixing solutions, mixing solutions being proceeded to 50mL is with in teflon-lined reactor, add a cover after screwing, in 180 DEG C of reaction 24h, prepare the solution containing CAg, this solution of centrifugation obtains solid formation, 2 times are washed respectively with deionized water and dehydrated alcohol, and it is dry at 60 DEG C, namely CAg carbon ball template is obtained, now the mol ratio of metal nanoparticle Ag and C is 5 × 10
-5: 1.
According to Sr
0.96ga
2s
4: Ce
0.04 3+ag
2.5 × 10the stoichiometric ratio of-4 pipettes 3.84mL1mol/LSr (NO
3)
2solution, 8mL1mol/LGa (NO
3)
3solution and 1.6mL0.1mol/LCe (NO
3)
3solution, is placed in 100mL beaker and forms nitric acid mixed solution, then takes CAg carbon ball template 240mg and adds in mixed solution, stir.Under magnetic stirring, above-mentioned mixed solution is added drop-wise in 40mL precipitation agent oxalic acid solution (0.5mol/L), then regulates pH to be 10 by ammoniacal liquor, after reaction 6h, through filtering, deionized water and washing with alcohol, obtain white mass, i.e. Sr after 80 DEG C of vacuum-drying 4h
0.96ga
2(C
2o
4)
4: Ce
0.04 3+cAg
2.5 × 10-4 precursor powders;
Presoma is ground, to be put in retort furnace in atmosphere in 800 DEG C of pre-burning 4h, carbon is converted into CO
2removing, in agate mortar, grinding evenly, is placed in corundum crucible, puts into stove, and first logical argon gas 15min, catches up with most air, then pass into H
2s, at 900 DEG C of calcining 6h, is cooled to 500 DEG C to stop H
2s changes argon gas, stops argon gas under normal temperature, takes out grinding and evenly namely obtains Sr
0.96ga
2s
4: Ce
0.04 3+ag
2.5 × 10-4 luminescent materials.
Fig. 1 is the luminescent spectrum comparison diagram under the obtained luminescent material of the embodiment of the present invention 4 and the cathode-ray exciting of comparative example luminescent material under acceleration voltage is 1.5KV; Wherein, curve 1 is the Sr being mixed with metal nanoparticle Ag prepared by the present embodiment 4
0.96ga
2s
4: Ce
0.04 3+ag
2.5 × 10the luminescent spectrum of-4 luminescent materials, curve 2 is Sr that comparative example is not mixed with metal nanoparticle Ag
0.96ga
2s
4: Ce
0.04 3+the luminescent spectrum of luminescent material.
As can be seen from Figure 1, at the emission peak at 450nm place, after clad metal nano particle the luminous intensity of luminescent material more not coated before enhance 19%.
Embodiment 5:Sr
0.9ca
2ga
2s
4: Ce
0.01 3+pt
5 × 10-3
Preparation containing Pt nanoparticle sol: take 25.9mg Platinic chloride (H
2ptCl
66H
2o) be dissolved in the deionized water of 17mL; Under the condition of magnetic agitation, 400mg Trisodium Citrate and 600mg sodium laurylsulfonate are dissolved in above-mentioned platinum acid chloride solution; Take 1.9mg sodium borohydride to be dissolved in 10mL deionized water, obtaining concentration is 5 × 10
-3the sodium borohydride solution of mol/L; Prepare 10mL concentration is 5 × 10 simultaneously
-2the hydrazine hydrate solution of mol/L; Under the condition of magnetic agitation, first in above-mentioned platinum acid chloride solution, drip the above-mentioned sodium borohydride solution of 0.4mL, after reaction 5min, then add the above-mentioned hydrazine hydrate solution of 2.6mL in above-mentioned platinum acid chloride solution, continue reaction 40min, obtaining 20mLPt nanoparticle concentration is 2.5 × 10
-3the colloidal sol of mol/L.
The preparation of CPt: take 0.0150g glucose and be dissolved in the alcoholic solution preparing glucose in the dehydrated alcohol of 30mL, above-mentioned for 10mL colloidal sol is added in the alcoholic solution of glucose, obtain mixing solutions, mixing solutions being proceeded to 50mL is with in teflon-lined reactor again, add a cover after screwing, in 150 DEG C of reaction 10h, prepare the solution containing CPt, this solution of centrifugation obtains solid formation, 2 times are washed respectively with deionized water and dehydrated alcohol, and it is dry at 70 DEG C, namely CPt carbon ball template is obtained, now the mol ratio of metal nanoparticle Pt and C is 5 × 10
-3: 1.
Take 14.7600gSrCO
3be dissolved in the Sr (NO that nitric acid obtains 100mL1mol/L
3)
2solution; Take 1.0009gCaCO
3be dissolved in the Ca (NO that nitric acid obtains 100mL0.1mol/L
3)
2solution; Take 15.9723gGa
2(CO
3)
3be dissolved in the Ga (NO that nitric acid obtains 100mL1mol/L
3)
3solution; Take 0.2301gCe
2(CO
3)
3be dissolved in the Ce (NO that nitric acid obtains 100mL0.01mol/L
3)
3solution.
According to Sr
0.9ca
0.09ga
2s
4: Ce
0.01 3+pt
5 × 10the stoichiometric ratio of-3 pipettes 3.6mL1mol/LSr (NO
3)
2solution, 3.6mL0.1mol/LCa (NO
3)
2solution, 8mL1mol/LGa (NO
3)
3solution and 4mL0.01mol/LCe (NO
3)
3solution, is placed in 100mL beaker and forms nitric acid mixed solution, then takes CPt carbon ball template 48mg and adds in mixed solution, stir.Under magnetic stirring, above-mentioned mixed solution is added drop-wise in 10mL precipitation agent oxalic acid solution (2mol/L), then regulates pH to be 10 by ammoniacal liquor, after reaction 3h, through filtering, deionized water and washing with alcohol, obtain white mass, i.e. Sr after 70 DEG C of vacuum-drying 5h
0.9ga
2(C
2o
4)
4: Ce
0.01 3+cPt
5 × 10-3 precursor powders;
Precursor powder to be put in retort furnace in atmosphere in 750 DEG C of pre-burnings 5 hours, carbon is converted into CO
2removing, then in agate mortar, grinding evenly, is placed in corundum crucible, puts into stove, and first logical argon gas 15min, catches up with most air, then pass into H
2s, at 1100 DEG C of calcining 3h, is cooled to 500 DEG C to stop H
2s changes argon gas, stops argon gas under normal temperature, takes out grinding and evenly namely obtains Sr
0.9ca
2ga
2s
4: Ce
0.01 3+pt
5 × 10-3 luminescent materials.
Embodiment 6:Sr
0.94ga
2s
4: Ce
0.06 3+(Ag
0.5/ Au
0.5)
1.25 × 10-3
Ag
0.5/ Au
0.5the preparation of nano particle colloidal sol: take 6.2mg hydrochloro-auric acid (AuCl
3hCl4H
2and 2.5mgAgNO O)
3be dissolved in the deionized water of 28mL; After dissolving completely, take 22mg Trisodium Citrate and 20mgPVP, and be dissolved under the environment of magnetic agitation in above-mentioned mixing solutions; Take freshly prepd 380mg sodium borohydride molten in 10mL deionized water, obtain the sodium borohydride aqueous solution that 10mL concentration is 1mol/L; Under the environment of magnetic agitation, the disposable sodium borohydride aqueous solution adding 0.3mL1mol/L in above-mentioned mixing solutions, continue reaction 20min afterwards, obtaining the total metal concentration of 30mL is 1 × 10
-3the Ag/Au nano particle colloidal sol of mol/L.
The preparation of C (Ag/Au): take the alcoholic solution that 0.7131g sucrose dissolved prepares sucrose in the dehydrated alcohol of 30mL, above-mentioned for 10mL colloidal sol is added in the alcoholic solution of above-mentioned sucrose, obtain mixing solutions, above-mentioned mixing solutions being proceeded to 50mL is with in teflon-lined reactor, add a cover after screwing, in 140 DEG C of reaction 15h, prepare the solution containing C (Ag/Au), this solution of centrifugation obtains solid formation, 2 times are washed respectively with deionized water and dehydrated alcohol, and it is dry at 80 DEG C, namely C (Ag/Au) carbon ball template is obtained, metal nanoparticle (Ag/Au) is 4 × 10 with the mol ratio of C
-4: 1.
According to Sr
0.94ga
2s
4: Ce
0.06 3+(Ag
0.5/ Au
0.5)
1.25 × 10the stoichiometric ratio of-3 pipettes 3.76mL1mol/LSr (NO
3)
2solution, 8mL1mol/LGa (NO
3)
3solution and 2.4mL0.1mol/LCe (NO
3)
3solution, is placed in 100mL beaker and forms nitric acid mixed solution, then takes C (Ag/Au) carbon ball template 150mg and adds in mixed solution, stir.Under magnetic stirring, above-mentioned mixed solution is added drop-wise in 20mL precipitation agent oxalic acid solution (1mol/L), then regulates pH to be 11 by ammoniacal liquor, after reaction 8h, through filtering, deionized water and washing with alcohol, obtain white mass, i.e. Sr after 90 DEG C of vacuum-drying 3h
0.94ga
2(C
2o
4)
4: Ce
0.06 3+c (Ag
0.5/ Au
0.5)
1.25 × 10-3 precursor powders;
Precursor powder to be put in retort furnace in atmosphere in 800 DEG C of pre-burnings 7 hours, carbon is converted into CO
2removing, then in agate mortar, grinding evenly, is placed in corundum crucible, puts into stove, and first logical argon gas 15min, catches up with most air, then pass into H
2s, at 950 DEG C of calcining 4h, is cooled to 500 DEG C to stop H
2s changes argon gas, stops argon gas under normal temperature, takes out grinding and evenly namely obtains Sr
0.94ga
2s
4: Ce
0.06 3+(Ag
0.5/ Au
0.5)
1.25 × 10-3 luminescent materials.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a preparation method for metal nano particle-doped alkaline earth thiogallate luminescent material, is characterized in that, comprise the steps:
Will containing after the salts solution of M ', the auxiliary agent playing dissemination and reductive agent hybrid reaction, obtained M ' nanometer particle colloid solution;
Described M ' nanometer particle colloid solution is added in the ethanol solution of sucrose or glucose, obtain mixing solutions, and the described mixing solutions confined reaction at 120 ~ 200 DEG C that will obtain, the obtained solution containing CM ', containing the solution of CM ' described in centrifugation, the solid phase obtained is washed, obtains CM ' carbon ball template after drying; Wherein, expression C coated M ', M ' and the mol ratio of CM ' carbon ball template are 1 × 10
-6: 1 ~ 0.4:1;
According to M
1-xga
2s
4: Ce
x 3+m '
yin each element chemistry metering ratio, measure M, the aqueous ethanolic solution of Ga and Ce salt, and then add described CM ' carbon ball template, stir, then oxalic acid precipitation agent is slowly added, obtain mixing solutions, then regulate the pH value of mixing solutions to be 10 ~ 12, after continuing stirring reaction 2 ~ 8h, filtration, washing, dry sediment, obtain M
1-xga
2(C
2o
4)
4: Ce
x 3+cM ' presoma; Wherein, CM ' carbon ball template and M
1-xga
2s
4: Ce
x 3+mol ratio be 0.025:1 ~ 10:1;
Grind described precursor powder even, under being placed in process furnace air atmosphere, in 500 ~ 800 DEG C of pre-burnings 1 ~ 12 hour, carbon is converted into CO
2removing, is cooled to room temperature, then grinds pre-sintered sample, grinding powder is placed in process furnace again, and pass into rare gas element in process furnace, makes to be inert atmosphere in process furnace; Then H is passed into
2s, at 800 ~ 1200 DEG C of calcining 2-10h, is cooled to 500 DEG C of stoppings to pass into H
2s, changes into and passes into rare gas element, under being cooled to normal temperature, stops passing into rare gas element, takes out sample, and evenly, obtain metal nano particle-doped alkaline earth thiogallate luminescent material, the chemical general formula of this luminescent material is M in grinding
1-xga
2s
4: Ce
x 3+m '
y;
In above-mentioned steps, M
1-xga
2s
4: Ce
x 3+for shell, M ' is kernel, represents coated, and M is at least one in Ca, Sr, Ba alkaline earth element, and M ', for metal nano particle-doped, is selected from least one in Ag, Au, Pt, Pd, Cu metal nanoparticle, and x is Ce
3+the mole number of ionic replacement M atom, the span of x is 0<x≤0.2, and y is M ' and M
1-xga
2s
4: Ce
x 3+mole ratio, the span of y is 0 < y≤1 × 10
-2.
2. the preparation method of metal nano particle-doped alkaline earth thiogallate luminescent material according to claim 1, it is characterized in that, described auxiliary agent is at least one in polyvinylpyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate or sodium laurylsulfonate; Described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride; The content of addition in M ' the nanometer particle colloid solution finally obtained of described auxiliary agent is 1 × 10
-4g/mL ~ 5 × 10
-2g/mL, the mol ratio of described reductive agent and M ' is 0.5:1 ~ 10:1.
3. the preparation method of metal nano particle-doped alkaline earth thiogallate luminescent material according to claim 1, is characterized in that, the time containing the salts solution of M ', auxiliary agent and reductive agent hybrid reaction is 10 ~ 45min.
4. the preparation method of metal nano particle-doped alkaline earth thiogallate luminescent material according to claim 1, it is characterized in that, the confined reaction of sucrose or glucose and M ' nanometer particle colloid carries out being with in teflon-lined reactor.
5. the preparation method of metal nano particle-doped alkaline earth thiogallate luminescent material according to claim 1, it is characterized in that, M, Ga and Ce salt is respectively M, the nitrate of Ga and Ce or acetate; In described aqueous ethanolic solution, the volume ratio of ethanol and water is 3 ~ 8:1.
6. the preparation method of metal nano particle-doped alkaline earth thiogallate luminescent material according to claim 1, is characterized in that, the mole dosage of described oxalic acid precipitation agent is for ensure to get M, Ga and Ce ion precipitates and excessive 25% completely; The pH value of mixing solutions being adjusted to 10 ~ 12 adopts ammoniacal liquor to regulate.
7. the preparation method of metal nano particle-doped alkaline earth thiogallate luminescent material according to claim 1, is characterized in that, in precursor power, and vacuum-drying 2 ~ 10h at described sedimentary drying is 60 ~ 100 DEG C.
8. the preparation method of metal nano particle-doped alkaline earth thiogallate luminescent material according to claim 1, is characterized in that, the span of x is 0.001≤x≤0.1, and the span of y is 1 × 10
-5≤ y≤5 × 10
-3.
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